Metalliferous polyazo dyestuffs



Patented Jan. 2%, 195

2,870,135 METALLIFEROUS POLYAZO DYESTUFF S .Otto Senn, Arlesheim, Basel, Switzerland, assignor, by mesne assignments, to Saul & Co., Newark, N; J., as nominee of "Fidelity Union Trust Company, executive trustee under Saudoz Trust No Drawing. Application January 17, 1955 SerialNo. 482,436

Claims priority, application Switzerland January 22, 6 Claims. (Cl. 260-145) The present invention relates to new and valuable metalliferous polyazo dyestuffs.

The said new dyestuffs of the present invention are obtained when (a) on the one hand, one mol of the diazo compound of an aminoazo dyestuif, obtained by coupling a diazomonoazo, a diazodisazo or a diazotrisazo compound, which contains in ortho-position to the diazo group a substituent which enables the formation of metal complex compounds, with a 1-amino-8-hydroxynaphthalene-monosulfonic acid or a 1-amino-8-hydroxynaphtha lene-disulfonic acid in the 7-position thereof, and (b) on the other hand, one mol of a diazo or a diazomonoazo compound, which contains in ortho-position to the diazo group a substituent which enables the formation of metal complex compounds, are coupled in any desired order of succession with one mol of 1,3-dihydroxybenzen'e, and the so-obtained polyazo dyestufi, whichcontains at least two and at most five sulfonic acid groups, is treated in substance with a metal-yielding agent; 1 1

Alternatively, the diazo compound (a) or the diazo compound (b) can be first coupled with the 1,3-dihydro'xybenzene, the so-obtained intermediate dyestufi treated with a metal-yielding agent, 'the metal complex compound then coupled with the diazo compound (6) or the diazo compound '(a'), and the 'so-obtained polyazo d'yestufi treated in substance with a metal-yielding agent.

The diazomonoazo, diazodisazo and diazotrisazo cfompounds/used according to the present invention in th'e preparation of diazo compounds (11) are themselves known and can be prepared in per se conventional manner. Such diazo compounds comprise for example the following aminoazo compounds.

3 methoxy 4 amino 6 methyl 4 7 hydroxy 1,1-

4 amino-'1,1' azobenzene-3,4"-disulfonic acidl-amino- Z-methoxy-S-methylbenzene, 4 amino1,1-azobenzene-3,4'-disulfonic acid-+1a-mino- 2-methoxynaphthalene-6 sulfonic acid, 2 (4-amino)phenyl-6-methylbenzthiazole-monosulfonic acid l-amino-2 methoxy--methylbenzene,

2 (4-arnino -phenyl-6-methylbenzthiazole-monosulfonic acid- 1-amino-2-methoxybenzene,

2 (4'-amino)-phenyl-6methylbenzthiazole-monosulfonic acid-i 1-amino-2-methoxy-S-acetylaminobenzene,

2 (4'-amino)-phenyl-6-methylbenzthiazole-monosulfonic acid-+1 amino-3-methylbenzene l-amino-2-methoxynaphthalene-6-sulfonic acid, r

2 (4-amino)-phenyl-6 methylbenzthiazole-monosulfonic acid' 1- amino-3-methylbenzene l -amino-Z-metho'xy- S-methylbenzene,

2 (4 amino) phenyl-6-methylbenzthiazole-disulfonic acid- 1 amino-3-methylbenzene 1-amino2-methoxy naphthalene-6-sulfonic acid, g

2 (4' amino) phenyl-6-methylbenzthiazole-disulfonic acid- 1 amino-3-methylbenzene l-amino-Z-methoxy- S-methylbenzene,

2 aminonaphthalene-4,8-disulfonic acid- 1 amino-3- methylbenzene-e 1 amino-2-methoxy-5-methylbenzene,

2 4 aminonaphthalene-6,8-disulfonic' acid- 1 amino-3- methylbenzenea 1-amino-2-methoxy-S-methylbehzene,

4 amino 4 nitro-l,l'-stilbene-2,2'-disulfonic acid- 1- aminQ-Z-methoxy-S-methylbenzene,

4 arnino 4 -'nitro-1,l'-stilbene-2,2'-disulfonic acid- 1- arriinO-Z-methoxynaphthalene-6-sulfonic acid,

1 carboxy 2 aminobenzene '5 sulfonic acid 1 4'- amino )-phe yl 3 methyl-5-pyrazolone, 1 amino 2- methoxy-iinethylbenzene,

l hydroxybenZene-Z-caiboXyIic acid 4,4'-diamino-1,1'-

diphenyl 1-amino-2-methoxy-5-methylbenzene,

1 hydroxybenzene-Z-carboxylic acid -4,4'-diamino-1,l' diphenyl- 1-amino 2 methoxynaphthalene-6-sulfonic acid,

1 hydroxybenzene-2-carboxylic acid 3,3' dimethoxy- 4,4 diamino 1,1 diphenyl- 1-amino-2-methoxy-5- methylbenzene,

1 hydroxybenzene-Z-carboxylic acid 3,3' dimethoxy- 4,4 diamino 1,1 diphenyl'- l-amino-Z-methoxynaphthalene-6-sulfonic aci 3,3 dimethoxy-4,4-diamino-1,1-diphenyl 1 hydroxybe'nzene-2-c2 1rboxylic acid, I I

1 hydroxybenzene 2 carboxylic acid 1-amino-4-(4- amino )'-benzoylaminobenzene l-amino 2 methoxy- S-methylbenzene,

1 hydroxybenzene 2 carboxylic acid +1-amino-4-(4 amino)-'benzoylaminobenzene l-amino 2 methoxynaphthalene-6-sulfonic acid,

1 amino 2 hydroxynaphthalene-4-sulfonic acid- 1- amino 3 hydroxybenzene 1 amino-Z-methoxy-S- methylbenzene,

1 hydroxybenzene 2 carboxylic acid l-amino-4-(4'- amino)-benzoylaminobenzene-2-carboxylic acid,

1 hydroxybenzene 2 carboxylic acid -1-amin0-4-(3- methyl-4'-amino) benzoylaminobenzene-Z-carboxylic acid, etc.

The coupling of the diazomonoazo, diazodisazo and diazotrisazo compounds to the 7-position of the l-amino- 8-hydroxynaphthalene-monosulfonic or disulfonic' acids the preferred ones being the 4-monosulfonic acid and the diazo compounds (a) is generally carried out by the if necessary in the presence of polymeric substances which indirect method. Illustrative of the amines which are contain imino or amino groups. The shades of the obsuitable for the preparation of the diazo compounds (b) tained dyeings vary within wide limits between blue, olive, are inter alia: khaki, brown and gray. The metal complex compounds 6 can be prepared in conventional manner and, most advantageously, by heating the aqueous dyestuff pastes or solutions with metal-yielding agents in the presence of alkali salts of low-molecular aliphatic carboxylic acids. The metals which are particularly suitable for preparing the metal complex compounds are nickel and especially copper.

The following examples and tables set forth presentlypreferred representative embodiments of the invention; these are intended to be solely illustrative and not at all limitative. In the examples the parts and percentages are by weight; the temperatures are in degrees Centigrade.

1-hydroxy-2-aminobenzene-4-sulfonic acid, 1-methoxy-2-aminobenzene-4-sulfonic acid, l-hydroxy-2-aminobenzene-4-sulfonic acid amide, 1-methoxy-Z-aminobenzeneA-sulfonic acid amide, l-hydroxy-2-amino-4-nitrobenzcne, 1-hydroxy-2-amino-4-nitrobenzene-6-sulfonic acid, l-hydroxy-2-aminoe4,6-dinitrobenzene, l-aminobenzene-2-carboxylic acid, 1-hydroxy-2-amino-6-chlorobenzene-4-sulfonic acid, 1-methoxy-2-amino-5-nitrobenzene, 1-methoxy-Z-amino-5-nitrobenzene-4-sulfonic acid, l-amino-2-hydroxynaphthalene-4-sulfonic acid,

1-amino-Z-methoxynaphthalene-6-sulfonic acid, EXAMPLE 1 v3-methoxy-4-amino-6-methyl -4-hydroxy 1,1 azobenzene-3'-carboxylic acid, 2 The tetrazo compound of 22.7 parts of 1-amino-4- 3 methoxy 4 amino-6-methyl-3'-carboxy-4'-hydroxy- (4-amino)-benzoylaminobenzene is coupled, in per se 1,1'-azobenzene-5-sulfonic acid, conventional manner, first in soda-alkaline solution with 3 methoxy 4 amino-6-methyl-l,1'-azobenzene-3'-sul- 13.8 parts of 1-hydroxybenzene-Z-carboxylic acid, and ionic acid, then in acetic acid solution with 13.7 parts of l-amino- 3 methoxy 4 amino-6-methy1-1,1'-azobenzene-4'-sul- Z-methoxy-S-methylbenzene. The so-obtained aminofonic acid, disazo compound is diazotized and coupled in weakly 3-amino-4-hydroxy-1,1'-azobenzene-3'-sulfonic acid, etc. alkaline solution with 31.9 parts of l-amino-S-hydroxynaphthalene-3,fi-disulfonic acid. Thereupon, 6.9 parts of sodium nitrite are added to the solution, which is then poured into parts of 30% hydrochloric acid-at 10''. Upon completion of the diazotization, the diazotrisazo compound is coupled, in soda-alkaline solution, with 11 parts of 1,3-dihydroxybenzene. The resultant tetrakisazo compound is isolated, dissolved in water together with 23 parts of sodium naphthalene-2-sulfonate, and the solution coupled in the presence of 50 parts of ammonia or 200 parts of pyridine with the diazo compound of 20.3 parts of 1-methoxy-Z-aminobenzene-4-sulfonic acid. R =N The obtained pentakisazo dyestuff is isolated and puri- 40 fied in conventional manner.

0H For conversion of the pentakisazo dyestuff into the copper complex compound, the moist filter cake is introduced N==NR at 8090 into a melt consisting of 100 parts of water,

parts of crystalline copper sulfate and 350 parts of crys- OH talline sodium acetate, after which the fusion is heated o and water distilled therefrom until a temperature of 107 wherein one R stands for the radical of a diazo is attained. Thereupon boiling is continued under re- Pound of an 311111102120 dyestufi, Obtained y Q P E a flux until the complex formation is completed, which rediazomonoazo. a diazodisazo or a diazotrisazo p n quires about 12-20 hours. In order to isolate the dyestutf, which contains in ortho-position to the diazo group a sub- 50 sufficicnt water is added to the fusion to enable the salts stituent which enables the formation of metal complex to go into solution while the dyestuff remains undissolved compounds, at the 7-position of a l-amino-S-hydroxyand is filtered ofi and dried. It corresponds to the formula The first coupling onto the 1,3-dihydroxybenzene can take place in (acetic) acid, neutral or weakly alkaline solution, while the carrying out of the second coupling generally requires, in addition to the presence of an alkaline agent such as ammonia or sodium carbonate, :1 diazo stabilizer such as naphthalene-Z-sulfonic acid and, in some cases, a coupling-enhancing agent such for ex- 35 ample as pyridine.

The polyazo dyestuffs according to the invention correspond, in the metal-free state to the formula l rrooc r a (|)--?u o 1 r=N 1 r=N- HoON=N C -o0-Nn N: QIEN- -o11 CH: H018 80:H SIQKH naphthalene-monosulfonic acid or a l-amino-S-hydroxyand dissolves with yellow-brown coloration in water and naphtha ene-disulfonic acid, and the other R stands for with red-brown coloration in concentrated sulfuric acid the radical of a diazo or a diazomcnoazo po d, and dyes cotton and fibers of regenerated cellulose in which contains in ortho-position to the diazo group a brownish khaki Shades offiutstanding fasmess t0 light substituent which enables the formation of metal comand good fastness t washing, to wet treatments and t0 plex compounds. The said dyestuffs can all be converted pel'splratloninto complex compounds by bivalent metals andin this EXAMPLE 2 form can be used as direct dyestuffs, the inherently good The pentakisazo dyestuff of Example 1 is also obtained properties of which can be still further improved by by converting the tetrakisazo compound into the copper after-treating the dyeings with salts of bivalent copper, complex compound with the aid of 25 parts of crystalline 2,870,135 v 6 copper sulfate, and then building up the pentakisazo dyeadded, and diazotization carried out by the addition of 30 stuff after the manner described in Example 1. By treatparts of 30% hydrochloric acid at The resultant diing the pentakisazo dyestuif with parts of crystalline azo compound is then coupled with 11 parts or" l;3"-'diliy'- copper sulfate, there is. obtained the end dyestufi which droxybenzene in the presence of 200 parts of sodium carcontains two atoms of copper in complex combination 5 bonate at 0". The so-produced green trisazo 'dycstuif is and which is identical with the end dyestufi of Example 1. precipitated with sodium chloride, then dissolved in 2000 Table 1, which follows, sets forth additional polyazo parts of water with the addition of 23 parts of naphthadyestuffs which can be prepared by coupling a diazo com lene-2-,sulf0nic c and 0 P m of am and c011- pound (a) and a diazo compound (b) with 1,3-dihydroxypled at 0 with the diazo compound of 20.3 parts of lbenzene, after the manner described in Examples 1 and 10 6 y-2- 0b 0 a e -O in d 2. In this connection, it is to be noted that, when prepar- Olive-dyed tetYakiSaZO dyesmfi is filtered Off and is P ing diazo components (a) from diazomonoazo. or diazofied y Yepfecipitation from hot waterdisazo or diazotrisazo compounds, which contain an end- For conversion of the Said tetrakisazo y f to positioned radical of 1-amino-2-alkoxynaphthalene 6-sulthe pp complex compound, the former is dissolved fonic acid, and from l-amino-8-hydroxynaphthalene- 1.5 in 3000 parts of water, after which 100 parts of sodium monosulfonic or disulfonic acids, it is very advantageous acetate and parts of crystalline copper sulfate are 1 dd a tertiary organic b h f example a pyriadded to the solution which is then heated in an enameled dine or quinoline. pressure vessel for 4 to 6 hours at 110-120, until the The polyazo dyestuffs are characterized by the diazo color haschanged to a dark brown. vThe dyestuff i's components (a) in column (B), the diazo components 20 then salted out with sodium chloride, filtered and dried (b) in column (C), and the shades of the coppered dye- It corresponds to the formula OTQ 'f-- Hoot I om c o I, l| 1= N: -tir=N- i I Hols -S O;H s ot];

ings and the dyeings with copper complex compounds in and is a dark powder which dissolves with dark brown column (D). coloration in water and with violetbrown coloration Table 1 Diazo components (a) Shade of dyeings 0! Example copper complex No. Diazo-rnonoor -disor -tr1s-azo 1-amine-S-hydroxy-naphtha- Drazo components ([2) compounds on compound lene-monoor -disulfonic acid 7 cotton .3 l-hydroxybenzene-Z-carboxylic. Lamino -8-hydroxynaphthe.- 1-methoxy-2-amino-5-nitro- Brown.

acid 4 1-arnino-4-(4- lane-3,6-disulfonie.acid. benzenei-sultonic acid. amino)-beuz0ylamln0bcnzene 1 amino-Z-methoxy- .S-methylbenzenc. *4 .do .do l-amino-Z-methoxynaphtha- Do.

lene-fi-sulfonic acid. .-5 do .do l-hydroxy-Z-aminobenzene-i- Brownish khaki.

sulfonic acid. *6 do .do l-hydroxy-2-amino-6-chl oro- Khaki.

, benzene 4-sulfouieacid. .7. do .do 1-hydroxy-2-amino-4-nitroben Do.

vzene-(S-sulfonlc acid. '8. .do .do 1-hydroxy-2-amino-4,6-dinitr0- Do.

benzene. t9- do ..do. l-amino-Z-hydroxynaphtha- Olive.

lene-4-sulfonic acid. .10 l-hydroxybenzene-Z-earboxylic .d0 1-methoxy-2-aminobenzene-4- Brown.

acid 1-amlno-"4-(4- sulfonic acid. amino)-henzoylamiuobenzene 1-amiu0-2-methoxynaphthalene-fi-sultonic acid. w r e 11 do l-amlno-S-hydroxynaphthal-hydroxy-z-amlno-4-nltroben- Do.

lene-4-sulfonic acid. "Zane-S-sulfonic acid." l-amino-S-hydroxynaphtha- 1-hydroxy-2ramino-4-nitroben- Do.

lane-3,6-disulfonlc acid. zene.

EXAMPLE 13 The disazo dyestulf, prepared in per se conventional concentrate? f g 3 fibers manner from 24.4 parts of tetrazotized 4,4'-diamino-3,3'- o regenerate: Ce u 056 m ast R s ades' xdimethoxyml, diphenyl of l hydl.roxybenzene Table 2 which follows ,sets forth additional polyazo 2-carboxylic acid and 31.9 parts of 1-amino-8-hydroxydy w p n pr p e after the manner descnbed naphthalene-3,6-disulfonic acid, is dissolved in 2000-parts in-Ekampleli The s'ignificances of B, C and D is the pf water after which 6.9 parts of sodium nitrite are same as in Table '1.

aqueous suspension of 1-amino-Z-hydroxy-S-methylbenzene is prepared by neutralizing a solution of 12.3 parts of the base in 50 parts of water and 13.5 parts of 30% hydrochloric acid by the dropwise 'additionof:13.8:parts: of aqueous 30% caustic soda solution.) Upon" completion of the coupling, the resultant monoazo compound is salted out, filtered and purified; It'is"thendissolv'ed in 400 parts of water with the addition of 6.9 parts of sodium nitrite and is indirectly diazotized with 28 parts of 30% hydrochloric acid in the presence of 75 parts of sodium chloride. The so-prepared diazo compound is filtered, stirred up with a small quantity of water and added at O-5 to a solution of 31.9 parts of 1'-amino-8- hydroxynaphthalene-3,6-disulfonic acid in 300 parts of water, 14 parts of aqueous 30% caustic soda solution, 20 parts of sodium carbonate and'Z'OOparts OfpyridineZ- Upon completion of the coupling, the formed green disazo compound is separated from the pyridine by precipitation with hydrochloric acid, dissolved. under; alkaline conditions in 400 parts of water, 6.9 parts of sodium nitrite added to the solution, and the whole poured into 45 parts of hydrochloricacidat- The-solutionis stirred until the ensuing diazotization is completed,

andthen the diazodisazo compound is coupled at 0 with a solution of 11 partsof l,3.-dihydroxybenzene.and 30.

parts of sodium carbonate in 200 parts of water. The so-obtained green trisazo compound is" precipitated'by the addition of sodium chloride at 70, is'filtered and is then dissolved in' 400 parts-of water and 200 parts of pyridine. A suspension, prepared in the usual way, of the diazo compound of 15.4 parts of l-hydroxy-Z-amino- 4-nitrobenzene is then run into the solution at 0". The formed tetrakisazo dyestuff is separated from the pyridine and is purified by reprecipitation. It is a dark powder which dissolves with'redcoloration in concentrated hydro- The copper-containing tetrakisazo dyestutf is then precipitated by the addition of sodium chloride to the copper- 'ing soliltion, after which the precipitated dye is filtered" oflf and finally dried. It corresponds to the formula (I -Cu and is a dark powder which yieldszfast brown dyeingson cotton. and .fibers of regenerated. cellulose."

EXAMPLE 37" acid reactionis neutralized by the' addition of sodium! dyestulf'swhich can be prepared acetate. Upon disappearance: ofithe' diazo compound,. the formed monoazo dyestuflt is filtered and is converted; into the difiiculty, solublesodiumsalt. This isdispersedn. in 500 parts of water, 6.9-parts of sodium nitrite are added, and diazotizationiis'. efiectedby theaddition Off 40 parts of concentrated hydrochloric acid; After severali. hours the diazo compoun'd 'islrunxinto-an; alkaline solutionl' of 31.9 parts of l-amino-8 hydroxy-naphthalene-3,6-disulfonic acid. Couplingto the disazo dyestufi t'akes place: fairly/"ra idly: To the solution of the gray-blue disazo dyestufi, 6.9 parts of sodium nitrite are added and dia-- zotization effected by means of aqueous hydrochloric acid. Coupling is. then carriedxout with a solution containing 11 parts of 1,3-dihydroxybenzene' and 30 parts of sodiurm. carbonate. The' obtained trisazo compound is coupled?- in the presence of 50.par'ts of ammonia withthediazo: solution of 20.3. partsof l-amino-2-methoxybenzenes4 sulfonic acid. The resultant pentakisazo dyestutf is iso--' lated and dried.

The said pentakisazo dyestuif can be converted into the copper complex compound after the manner set forth:v in Example 1. The copper complex compound thus: prepared corresponds to the formula and is a dark powder which dissolves with dark brown coloration in Water and with violet-red coloration in concentratedsulfuric acid, and dyes. cotton and fibers of regenerated cellulose in dark brown shades withg good fastness to light and to washing. 7

Table 3 which follows sets. forth additional. polyazo in the manner described in Examples 36 and 37. In such table, columns B, C. and D have the same significance as in Table .1.

i Tabled Example No.

2 (4'-amtno) phcnyl 6 methylbenzthlazolc-sulfonlc acid 1 methoxy 2 amtnobcnzene.

2-(4'-amino) phenyl 6 mothylhenzthlazole-sulionic acid -r 1 methoxy 2 amino-4-acetylaminobenzene.

2 (4-amino) phenyl 6 methylbenzthiazolo-sullonlc acid l-methoxy 2 amino- 4-methylhenzono.

2 (4'-amin0) phenyl 6 methylbenzthlaz0ie-3-sullonic acid 1-methoxy 2 amino- 4-methylhenzene.

l-amino 4 hydroxybcnzenc -3 carboxylic acid Lamino 2 mcthoxy methylbenzene.

l-amino 2 hydroxy 3 carboxybenzene-5-sulfonic acid -r 1- amlno 2 methoxyfi-methylbenzene.

1- amlno 2 hydroxy naphthalene-tsulfonic acid 1- amino -3 -hydroxyhcnzene l-arnino-z-methoxy fimethylbenzene.

l-amino 2 hydroxybenzene 5- sultonle acid -s 1-(4'-amln0)-phenyl 3 mcthyl- 5-pyrazolone 1- amino 2- methoxy-fi-rnetuylbenzene.

1- aminonaphthalene 4,8-dl5ul- Ionic acid -0 1- amtno'smethylbenzene bamino 2 methoxy 5 methylbenzene.

4 amino 4-nltro -1,1'stilbene 2,2'- dlsulionle acid 1- amlno 2 methoxynaphthalene-fi-sullonic acid.

1 amino 8 hydroxy naphthalene 3,6 disulionic acid.

rln

1 methoxy 2 arnlnobenzenc- Brown.

fi-sull'onic acid.

1 hydroxy 2 amino 4 nitrohcnzene.

..---do Blue.

l-methoxy 2 -amlnobenzene- Brown.

4-sulfonlc acid.

l-hydroxy 2 amino 4-nltrobenzene.

1-methoxy-2-amln0bcnzene---.

EXAMPLE 48 The nickel complex compound of the metal-free dyestuif described in Example 1 is obtained when such dyestufi is treated in accordance with the said example, but replacing the 50 parts of crystalline copper sulfate by 56 parts of crystalline nickel sulfate. The nickel-containing pentakisazo dyestufi corresponds to the formula noon and is a dark powder which dyes cotton and fibers of regenerated cellulose in olive shades.

EXAMPLE 49 The nickel complex compound of the tetrakisazo dyestufi described in Example 13 can be prepared after the manner set forth in Example 48. This nickel complex compound corresponds to the formula CHzO 0Ni 0 Hood and dyes a more yellowish brown than the corresponding copper complex compound, being distinguished by its outstanding light fastness.

In essentially similar manner, nickel complex com- 4.5 pounds may be prepared corresponding to any of the other copper complex compounds herein disclosed.

By coupling in the presence of pyridine the diazodisazo 60 compound prepared according to Example 36 with the monoazo compound prepared in conventional manner from 18.9 parts of diazotized 1-hydroxy-2-aminobenzene- 4-sulfonic acid and 11 parts of 1,3-dihydroxybenzene, a tetrakisazo dyestuff is obtained which dyes cotton and fibers of regenerated cellulose in fast gray shades by the aftercoppering process. Its solution in water and in con- SO;H

i3 centrated'sulfuric acid is greenish gray. The copper-com"- plex compound, which correspondsto the formula" scan. 7 g s o e'u 0H i N/ on, Hogsis obtainedt after the manner described in Example 36.

of ice water, and the resultant suspension added at 0 to a solution of 3'l.9 parts of l-amino-8-hydroxynaphthalene 3,6-disulfonic acid in 200 parts of water, parts of 25% aqueous ammonia and' 300 parts of pyridine. Upon completion of the coupling' the formed green trisa'zo compound is precipitated by acidification;- and isth en filtered and dissolved, under alkaline, conditions, in 1000 partsof water. 6.9 partsofsodium nitrite are added to the solution, after which the latter is added at 10 to parts of 30% hydrochloric acid. After several hours, the obtained diazo compound is filtered and stirred into 200 parts of ice water. The resultant suspension is added at.0 to a solution, in 200 partsofswaterand:200 parts of pyridine, of the copper complex compound of. the

monoazo dyestufi, prepared bycoupling 1-hydroxy-2- 0 aminobenzene-4-sulfonic acid with 11 parts of 1,3-dihydroxybenzene.

The so-prepared pentakisazo dyestufif is isolated, purified, and converted into its complex copper compound after the manner set forth in Example 1, employing 25 parts of crystalline coppersulfate. The copper-containing'dyestufi corresponds to the formula 803E and is.a dark powder which dissolves with green coloration in water and dyes cotton and fibers of regenerated cellulose in fast olive shades.

EXAMPLE 5 2 17.2 parts of 1-aminobenzene-3-sulfonic acid' are diazotized in conventional manner, employing 6.9, parts of sodium nitrite and 25 parts of concentrated hydrochloric 114? acid. The diazo mass is' cbrhbinedwith an' al'kalihe'isolu tion' of"l5;1 parts of 1-hydroxyg2+acetylaminobenzene:

O-'-Cu 0* soan S0311 By boiling the solution ina 1 aqueousysodium hydroxide' solution, theacetyl groupof thefOrmed monoazo;

compound is split 0E! The thus-prepared aminoaz'o come pound is precipitated by the additionof 'li'yd'roehloficacid to the solution and is then filtered. It is dissolved by the addition of alkali hydroxide, 6.9 parts of sodium nitrite are added to the solution,;which is then run into 30 parts of concentrated hydrochloric acid. The resultant solution of the diazoazocompound is coupled with a strongly alkaline solution of 11 parts of 1,3-dihydroxybenzene. The so-prepared disazo compound precipitated with the .aid of; sodium chloride; isscoupled, .in,-tl1e;.formof a 20% pyridine solution, with the diazodisazo compound, prepared according to Example 37, of 32 parts of 2-(4'-amino)-phenyl 6 methylbenzthiazole monosulfonic acid, 13.7 parts of 1-amino-2-methoxy-5methylbenzene and 31.9.parts of 1-amino-8-hydroxynaphthalene- 3,6-disulfoniclacid. The pentakisazo dyestulf, thus obtained, is" freed-.0f pyridine and is purified by reprecipita- 30 tion from hot water.

The corresponding copper complex compound is prepared after the manner set forth in Example 1. It corre sponds to the formula and dissolves with gray coloration in water and with violet coloration in concentrated sulfuric acid, and dyes cotton and fibers of regenerated cellulose in fast gray shades.

EXAMPLE 53 parts of cotton are entered at room temperature (about 20-30) into a solution of 0.6 part of the dyestuff prepared according to Example 13, and 2 parts of trisodium phosphate (or sodium metaphosphate or trisodium 55 polyphosphate) in-3000 parts of .water, with the addition of 10 parts of Glaubers salt.. The dyebath is heated to boilingtemperature in-the course'of30 minutes. During HOzS- SOaH such heating, an additional 10 parts of Glaubers salt are added. Dyeing of the cotton is carried out at boiling temperature for;15 minutes. At the end of this time, 20 more parts-of Gla'uberssalt are added; after which the dyeing is completed in the course of 15-20 minutes in the cooling bath. The cotton is withdrawn from the bath, is thoroughly rinsedand dried. It is dyed in a black-brown shade.

The fastness properties of the dyeing can be further enhanced by a treatment with a copper-containing polyalkylenepolyamine. To this end, 100 parts of dyed and dried cotton are introduced at 30 into a bath consisting of 3000 parts of water and 2 parts of a copper-containing polyalkylenepolyarnine. The bath is heated to 70 and the dyed cotton is kept therein for 30 minutes. Thereupon the dyed and treated cotton is rinsed and dried. Its shade remains unchanged.

Having thus disclosed the invention what is claimed is:

1. A metal complex compound selected from the group consisting of copper and nickel complex compounds of polyazo dyestuffs which correspond in the metal-free state to the formula R-N=N 15 N=N-R H wherein one R stands for the radical of a diazo comnooc cmo H00? CHsG pound of an aminoazo dyestuff, obtained by the coupling of a member selected from the group consisting of a diazomonoazo, a diazodisazo and a diazotrisazo compound, each of the said compounds containing as components aromatic radicals selected from the group consisting of radicals of the benzene, naphthalene, diphenyl, stilbene, pyrazolone and benzthiazole series, and including in the ortho-position to the diazo group a substituent selected from the group consisting of hydroxy, rnethoxy and carboxy, with a member selected from the group consisting of a l-amino-S-hydioxynaphthalene-monosulfonic acid and a 1-amino-8-hydroxynaphthalene-disulfonic acid in the 7-position, and the other R stands for a member selected from the group consisting of radicals of diazo and diazomonoazo compounds, each of the said compounds containing as components aromatic radicals selected from the group consisting of radicals of the benzene and naphthalene series, and including in the ortho-position to the diazo group a substituent selected from the group consisting of hydroxy, methoxy and carboxy.

2. The polyazo dyestuff which corresponds to the formula 3. The polyazo dyestuff which corresponds to the formula CH; H0 8- SOsH H0 8 EON:

4. The polyazo dyestufi which corresponds to the 5. The polyazo dyestufi which corresponds to the formula i N=N H028- 803E B0 11 17 1 8 6. The polyazo dyestufi which corresponds to the formula o-( :u 0 /SO3H l s O--Cu o N=N N=N 0 1 CA N=N N=N H0 CH3 HOaS- 80:11 E

soar! References Cited in the file of this patent UNITED STATES PATENTS 2,673,200 Ruckstuhl et a1. Mar. 23, 1954 OTHER REFERENCES Venkataraman: Synthetic Dyes, vol. I, p. 523.

UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,870,135 January 20, 1959 Otto Senn It is hereby certified that error appears in the above numbered patent requiring correctlon and that the said Letters Patent should read as corrected below.

Column 1, line 62, for acid+1a-minoread acid 1-aminocolumn 10, lines 51 to 66 inclusive, Example 37, right-hand portion of the formula should appear as shown below instead of as in the patent:

Signed and sealed this 28th day of July 1959.

Attest: v KARL I-I. AXLINE, ROBERT C. WATSON,

Attesting Oyficer. commissioner of Patents. 

1. A METAL COMPLEX COMPOUND SELECTED FROM THE GROUP CONSISTING OF COPPER AND NICKEL COMPLEX COMPOUNDS OF POLYAZO DYESTUFFS WHICH CORRESPOND IN THE METAL-FREE STATE TO THE FORMULA 